Study of the formation of structures in solutions of chitosan – polyvinyl alcohol polymer blends

The aim of this work was the investigation of the formation of structures in solutions of individual polymers, as well as their blends with each other in buffer solvents with different values of pH. In this study we used a sample of chitosan (degree of deacetylation ~ 84 %, M = 130,000), which is a polycation when dissolved, and polyvinyl alcohol (r = 1.25 g/cm3, M = 5000). Buffer systems based on acetic acid and sodium acetate with pH = 3.8, 4.25, and 4.75 were used as solvents. Viscosimetry was used to determine the intrinsic viscosity, the degree of structuring, and the Huggins constant. The Kriegbaum method was used to determine the nature of the aggregates formed by the blend of the studied polymers. In the course of the research, it was shown that an increase in the pH of the acetate buffer used as a solvent was accompanied by a compression of the macromolecular coil (a decrease in intrinsic viscosity values), a deterioration in the quality of thesolvent (an increase in Huggins constant values), and an increase in the degree of polymer aggregation in a solution for chitosan polyelectrolyte. At the same time for a solution of polyvinyl alcohol the pH of the buffer practically did not affect the nature of the polymer-solvent interaction. It has been proved that polymer blends are characterized by an increase in aggregation processes and a decrease in the thermodynamic quality of the solvent in comparison with solutions of individual polymers. The size of the “combined” macromolecular coil, characterized by the intrinsic viscosity value for the polymer blend, which can be both above (buffer solvent with pH = 3.80) and below (buffer solvent with pH = 4.25 and 4.75) additivevalues, changed depending on the type of formed polymer-polymer aggregates (homo- or hetero-). It was established that the type of aggregates (homo- or hetero-) formed in solutions of polymer blends was determined not only by the thermodynamic quality of the used solvents, but also by the concentration of the polymers in the initial solutions

Evaluation of Microbe-Driven Soil Organic Matter Quantity and Quality by Thermodynamic Theory

ABSTRACT Microbial communities, coupled with substrate quality and availability, regulate the stock (formation versus mineralization) of soil organic matter (SOM) in terrestrial ecosystems. However, our understanding of how soil microbes interact with contrasting substrates influencing SOM quantity and quality is still very superficial. Here, we used thermodynamic theory principles and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) to evaluate the linkages between dissolved organic matter (DOM [organic substrates in soil that are readily available]), thermodynamic quality, and microbial communities. We investigated soils from subtropical paddy ecosystems across a 1,000-km gradient and comprising contrasting levels of SOM content and nutrient availability. Our region-scale study suggested that soils with a larger abundance of readily accessible resources (i.e., lower Gibbs free energy) supported higher levels of microbial diversity and higher SOM content. We further advocated a novel phylotype-level microbial classification based on their associations with OM quantities and qualities and identified two contrasting clusters of bacterial taxa: phylotypes that are highly positively correlated with thermodynamically favorable DOM and larger SOM content versus those which are associated with less-favorable DOM and lower SOM content. Both groups are expected to play critical roles in regulating SOM contents in the soil. By identifying the associations between microbial phylotypes of different life strategies and OM qualities and quantities, our study indicates that thermodynamic theory can act as a proxy for the relationship between OM and soil microbial communities and should be considered in models of soil organic matter preservation. IMPORTANCE Microbial communities are known to be important drivers of organic matter (OM) accumulation in terrestrial ecosystems. However, despite the importance of these soil microbes and processes, the mechanisms behind these microbial-SOM associations remain poorly understood. Here, we used the principles of thermodynamic theory and novel Fourier transform ion cyclotron resonance mass spectrometry techniques to investigate the links between microbial communities and dissolved OM (DOM) thermodynamic quality in soils across a 1,000-km gradient and comprising contrasting nutrient and C contents. Our region-scale study provided evidence that soils with a larger amount of readily accessible resources (i.e., lower Gibbs free energy) supported higher levels of microbial diversity and larger SOM content. Moreover, we created a novel phylotype-level microbial classification based on the associations between microbial taxa and DOM quantities and qualities. We found two contrasting clusters of bacterial taxa based on their level of association with thermodynamically favorable DOM and SOM content. Our study advances our knowledge on the important links between microbial communities and SOM. Moreover, by identifying the associations between microbial phylotypes of different life strategies and OM qualities and quantities, our study indicates that thermodynamic theory can act as a proxy for the relationship between OM and soil microbial communities. Together, our findings support that the association between microbial species taxa and substrate thermodynamic quality constituted an important complement explanation for soil organic matter preservation.

Synthesis of Narrowly Dispersed Block Copolymer of Butyl Acrylate and Acrylic Acid in a Solution Acquiring Colloidal Properties during Cooling

The homophase polymerization of acrylic acid is carried out in a solution of poly(butyl acrylate) trithiocarbonate (PBATC) in a mixed solvent 2-propanol–water. The phase diagram of the three-component PBATC-2-propanol–water system at 22°C is obtained. The homophase region of the compositions of semidilute solutions is determined. The homophase polymerization of AA in the three-component system at 70°C, in which the mixed solvent with respect to PBATC is similar in thermodynamic quality to the θ-solvent at 22°, yields solutions of the narrowly dispersed block copolymer butyl acrylate–acrylic acid. The content of the block copolymer in solutions is 15–23%, the MW of the copolymer is 10–20 × 103, and the polydispersity coefficient is 1.12–1.16. As evidenced by dynamic light scattering, under normal conditions, the solutions contain nanoparticles with a diameter of up to 50 nm with a narrow size distribution.

Self-Assembly of Molecular Brushes with Polyimide Backbone and Amphiphilic Block Copolymer Side Chains in Selective Solvents

Three-component molecular brushes with a polyimide backbone and amphiphilic block copolymer side chains with different contents of the “inner” hydrophilic (poly(methacrylic acid)) and “outer” hydrophobic (poly(methyl methacrylate)) blocks were synthesized and characterized by molecular hydrodynamics and optics methods in solutions of chloroform, dimethylformamide, tetrahydrofuran and ethanol. The peculiarity of the studied polymers is the amphiphilic structure of the grafted chains. The molar masses of the molecular brushes were determined by static and dynamic light scattering in chloroform in which polymers form molecularly disperse solutions. Spontaneous self-assembly of macromolecules was detected in dimethylformamide, tetrahydrofuran and ethanol. The aggregates size depended on the thermodynamic quality of the solvent as well as on the macromolecular architectural parameters. In dimethylformamide and tetrahydrofuran, the distribution of hydrodynamic radii of aggregates was bimodal, while in ethanol, it was unimodal. Moreover, in ethanol, an increase in the poly(methyl methacrylate) content caused a decrease in the hydrodynamic radius of aggregates. A significant difference in the nature of the blocks included in the brushes determines the selectivity of the used solvents, since their thermodynamic quality with respect to the blocks is different. The macromolecules of the studied graft copolymers tend to self-organization in selective solvents with formation of a core–shell structure with an insoluble solvophobic core surrounded by the solvophilic shell of side chains.

The Effects of Boundary Design on the Efficiency of Large-Scale Hot Water Heat Stores

Boundary design of stratified hot water heat stores is important not only to minimize the thermal losses to the ambient but also to preserve the thermodynamic quality of the stored energy. A new method of characterization, which equivalently accounts for both these concerns, is applied in this paper to investigate into the boundary design of large-scale hot water heat stores. A variety of concepts related to general design of the containments, namely, the effects of the thermal conductivity and thickness of the container wall, are numerically analyzed. The design insights provided by the analysis are in good agreement with the corresponding experimental results for small-scale hot water heat stores found in the literature. Different ways of insulation application, differential application of the external insulation, and insulation of the top walls are further investigated to obtain ideas for the efficient use of the insulation material. The new characterization scheme proves to be an efficient tool to rank the performance of different boundary designs during storing process of large-scale stratified hot water heat stores and to provide valuable design insights.